CN111468109A - Needle-like alumina carrier - Google Patents
Needle-like alumina carrier Download PDFInfo
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- CN111468109A CN111468109A CN202010318747.7A CN202010318747A CN111468109A CN 111468109 A CN111468109 A CN 111468109A CN 202010318747 A CN202010318747 A CN 202010318747A CN 111468109 A CN111468109 A CN 111468109A
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- alumina
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 239000010703 silicon Substances 0.000 claims abstract description 28
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 13
- 239000011737 fluorine Substances 0.000 claims abstract description 13
- 229910052709 silver Inorganic materials 0.000 claims abstract description 13
- 239000004332 silver Substances 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 6
- 229940096017 silver fluoride Drugs 0.000 claims abstract description 5
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims abstract description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 30
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 29
- 238000005260 corrosion Methods 0.000 claims description 26
- 230000007797 corrosion Effects 0.000 claims description 26
- 239000011148 porous material Substances 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 18
- 229910001868 water Inorganic materials 0.000 claims description 18
- 238000011049 filling Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 239000002210 silicon-based material Substances 0.000 claims description 14
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005234 chemical deposition Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000005530 etching Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 229910021426 porous silicon Inorganic materials 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 1
- 239000002585 base Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 7
- -1 silver ions Chemical class 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 229910004074 SiF6 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000026058 directional locomotion Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/12—Fluorides
-
- B01J35/613—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a needle-punched alumina carrier, which is prepared by coating alumina on the surface of porous silicon serving as a template, roasting, and discharging fluorine gas out of the silicon template, wherein the needle-punched alumina carrier is prepared by the distribution of 20-40 needles per mu m215-25nm of needling tip, 130-150nm of distance between adjacent needling tips, 5-8 μm of alumina needling height and 10-13 m of specific surface area2The alumina carrier is prepared by a template method, and silver or silver fluoride particles are attached to the vicinity of the tip of the alumina.
Description
Technical Field
The invention relates to a needle-punched alumina carrier, belongs to the field of catalyst carrier preparation, and is particularly suitable for the field of gas-solid phase reaction.
Technical Field
Alumina is widely used industrially as a very important catalyst carrier and adsorbent. The porous alumina has the outstanding characteristics of high specific surface area, large pore diameter, ordered mesopores and the like besides the excellent performance of common alumina, and becomes a hot spot of research in recent years.
The conventional porous alumina materials are produced by various methods, such as substitution method, foaming method (generally, bubbles are generated by a foaming agent or reduced pressure to form disordered macropores, but the pore diameter and pore type are not uniformly distributed and are limited), and template method. Among them, the template method is attracting attention and favored by its simple preparation process, controllable pore shape and structure. The method takes a material with a micro-ordered structure as a template, fills a target raw material in a gap part of the template, and removes the template by high-temperature pyrolysis or chemical treatment after a framework is formed to finally or orderly form the macroporous material. At present, a biological template method and an ordered gel microsphere method are mature. In the preparation process, the material of the template, the method for removing the template and the formed hole pattern are clearly understood. For example, the template is easy to prepare, the template material should have certain stability, the target porous material is not affected in the process of removing the template, and the template is easy to remove.
The preparation method comprises the steps of (1) preparing an integral alumina sol by taking styrene and divinylbenzene as monomers in a CN 101612581A, uniformly mixing azodiisobutyronitrile serving as an initiator with the mass being 2-20% of the total monomer mass and an Al catalyst with the mass being 0.1-2% of the total monomer mass to obtain an oil phase, adding deionized water into the oil phase under stirring to enable the volume fraction of the water phase to be 80-90% to obtain a reversed phase concentrated emulsion, pouring the concentrated emulsion into a mold, carrying out sealed polymerization at 50-80 ℃ for 24-48 h, drying at 60-90 ℃ for 24-48 h to obtain an integral type organic macroporous template, (2) preparing the alumina sol by taking pseudo-boehmite as a precursor, grinding 3-6 mg pseudo-boehmite, adding the ground pseudo-boehmite in batches to 60-90M L deionized water, stirring for 0.5-2 h to uniformly disperse, adding the prepared pseudo-boehmite sol into a suspension by slowly adding the pseudo-boehmite sol, wherein the pseudo-boehmite sol is 0.5 mol 4-1 mol/1 mol, adjusting the pseudo-boehmite sol to 3M L min, stirring for 0-2 h, drying at a constant temperature rate of the temperature of the Al catalyst, adding the porous alumina sol, drying rate of the Al catalyst, adding the Al catalyst, stirring speed of the Al catalyst, drying at room temperature, drying at a constant temperature of a slow rate of a slow drying method, a slow drying method.
Disclosure of Invention
Based on the problems in the prior art, the invention provides a needle-punched alumina carrier, and the needle-punched distribution of the needle-punched alumina is 20-40 pieces/mu m215-25nm of needling tip, 130-150nm of distance between adjacent needling tips, 5-8 μm of alumina needling height and 10-13 m of specific surface area2The alumina carrier is prepared by a template method, and silver or silver fluoride particles are attached to the vicinity of the tip of the alumina.
Further, the preparation process of the template method is as follows: (1) pretreating a silicon-based material; (2) chemically depositing Ag particles on the surface of the silicon; (3) catalyzing and corroding a silicon material by Ag particles to obtain corrosion holes; (4) corroding and reaming the hole; (5) filling alumina silica sol into the corrosion hole; (6) roasting at high temperature; (7) repeating the steps (5) and (6); (8) the fluorine gas removes the silicon substrate.
Further, the process for pretreating the silicon-based material in the step (1) comprises the following steps: cutting a monocrystalline silicon wafer to a proper size, then carrying out ultrasonic cleaning by ethanol, acetone and deionized water in sequence to remove oil stains, repeating the cleaning for 1-3 times, then soaking for 10min by 10-15wt% of hydrofluoric acid to remove an oxide layer, washing by deionized water, and drying under an inert atmosphere.
Further, the chemical deposition process of Ag particles on the silicon surface in the step (2) is as follows: the chemical deposition liquid is water solution of silver nitrate and hydrofluoric acid, the volume ratio of AgNO3 to HF to H2O is 1: 2-3: 4-8, and the temperature is 30-35oC, the time is 1-2 min.
Further, the technological parameters of Ag particles for catalyzing and corroding silicon materials in the step (3) are as follows: the corrosive liquid is aqueous solution of hydrofluoric acid and hydrogen peroxide, the concentration of HF is 0.3-0.45M, and H is2O2The concentration of the catalyst is 0.3-0.4M, the time is 60-80min, the temperature is normal temperature, the catalyst is washed by ionized water after being corroded, and the catalyst is dried and oxidized by air.
Further, the parameters of the corrosion reaming in the step (4) are as follows: the oxidation temperature is 700 deg.CoAnd C, forming disordered silicon oxide on the surface of the monocrystalline silicon for 30-40min, then cooling and soaking in 10-15wt% hydrofluoric acid for 10min to remove an oxide layer, and repeating the etching and reaming step for 1-3 times to obtain the large-aperture etched hole.
Further, the process of filling alumina silica sol into the corrosion hole in the step (5) is as follows: adding 3-5 g of pseudo-boehmite into deionized water in batches under the stirring condition, adding 1.5-2M HNO3 to obtain alumina hydrosol, continuously stirring for 2-3 h, soaking the hole-expanded base material obtained in the step (4) into the alumina sol, vacuumizing, and filling the alumina sol on the surface of the pore channel.
Further, the high-temperature roasting parameter in the step (6) is 300oDrying under nitrogen protection for 20-30min, and then 1-2oC /min-1Heating to 1100-1300 ℃, drying at constant temperature for 1-2h, and naturally cooling.
Further, the step (7) is repeated for 2 to 4 times.
Further, the heating temperature for removing the silicon substrate by the fluorine gas in the step (8) is 35 to 40oC, the time is 1-2 h.
Further, the application of the needle-punched alumina carrier is characterized by being applied to the field of gas-solid phase catalytic reaction.
The reagents, concentrations, and principles used in the above needle-like alumina carrier and the preparation method of the carrier are explained in detail as follows:
(1) the silicon-based material is pretreated by cutting a monocrystalline silicon wafer to a proper size, then ultrasonically cleaning the monocrystalline silicon wafer by ethanol, acetone and deionized water in sequence to remove oil stains, repeatedly cleaning for 1-3 times, then soaking the monocrystalline silicon wafer in 10-15wt% hydrofluoric acid for 10min to remove an oxide layer, washing the pretreated monocrystalline silicon wafer by deionized water, and drying the pretreated monocrystalline silicon wafer in an inert atmosphere.
No matter what kind of surface treatment process, good effect is to be obtained, surface pretreatment is the primary condition, mainly because the oxidation film and grease on the surface of the single crystal silicon can cause subsequent silver ions to be unable to contact with the silicon substrate and to be unable to reduce and deposit the silver ions if the oxidation film and grease can not be effectively removed, and further can not cause subsequent catalytic corrosion, if the grease can not be removed, the silver ions can be caused to be unevenly distributed in the chemical deposition process, and the agglomeration phenomenon of the silver ions, namely the existence of the oxidation film and grease can seriously affect the pore channel distribution of the porous silicon template, in addition, the drying should be inert atmosphere drying, so as to avoid the introduction of oxidizing gas and the formation of an oxidation layer on the surface.
(2) Chemical deposition of Ag particles on silicon surface: the process for chemically depositing Ag particles on the silicon surface in the step (2) is as follows: the chemical deposition liquid is water solution of silver nitrate and hydrofluoric acid, the volume ratio of AgNO3 to HF to H2O is 1: 2-3: 4-8, and the temperature is 30-35oC, the time is 1-2 min.
The process is that Ag is chemically deposited on the surface of crystalline silicon, a large number of Si-H bonds are formed on the surface of the silicon wafer after HF treatment, the Si-H has strong reducibility, Ag + in silver nitrate has strong oxidizability, the Ag + and the Ag + are subjected to redox reaction, Ag + electrons are reduced into Ag atoms and are deposited on the surface of the Si wafer in a nanoparticle form to form a discontinuous Ag particle film, and the size and the spacing of Ag particles directly determine the size and the spacing of a pore channel.
In the invention, the concentration of AgNO3 is preferably controlled to be 2-3mM, the silver plating time is within 1-2min, the size is generally distributed within the range of 100-300 nm, Ag particles are uniformly distributed on the surface of the whole substrate, the concentration of Ag ions in silver nitrate is strictly controlled, if the concentration of the Ag ions is too high, too many corroded points and too dense pore channels are caused, and subsequent filling is not facilitated, and if the concentration of the Ag ions is too low, the pore channels are too sparse, and the subsequent filling is also not facilitated.
Furthermore, it is common for the catalytic metal selected to be Ag, rather than Au or Pt. Ag and Au are commonly used catalytic metals that can etch vertically down in a specific direction, but for Pt particles, the motion is complex, and it has been reported that a vertical, spiral, non-directional motion trajectory is observed.
The method is mainly based on the selection consideration of active components in the subsequent catalyst preparation process, and in addition, the deposition size control of Ag is mature, and uniform pore channels are easy to form.
(3) Catalyzing and corroding silicon material with Ag particle to obtain corroded hole, where the corrosive liquid is aqueous solution of hydrofluoric acid and hydrogen peroxide, HF concentration is 0.3-0.45M, and H is2O2The concentration of the catalyst is 0.3-0.4M, the time is 60-80min, the temperature is normal temperature, the catalyst is washed by ionized water after being corroded, and the catalyst is dried and oxidized by air.
The Ag particles act as a catalyst, and the Si under the Ag particles is oxidized to SiO2 by the oxidizing agent (e.g., H2O2) in the etching solution and dissolved by HF, causing the Ag particles to sink, and thus, the Si is gradually etched down to form "tunnels" at the locations covered by the Ag particles. Since the Ag particle film is discontinuous, the voids between adjacent Ag particles are not etched, resulting in the formation of silicon nanowires between adjacent "tunnels". The reaction equation involved in etching is as follows:
2Ag+H2O2+2H+→2Ag++2H2O;
Si +4Ag++6F-→4Ag+SiF6 2-;
Si0+ 2H2O2+ 6F-+ 4H+→SiF 62-+ 4H2O;
further, HF, H2O2The concentration of (a), the etching time, is critical to the shape of the channel and whether the channel is etched vertically,
α = HF/(HF + H) is generally used2O2) The channel structure is evaluated, if α is between 0.7 and 1, the eroded hollow is cylindrical, if α is between 0.2 and 0.7, a tapered hollow is obtained, when α is below 0.2, there are few obvious channels, HF and H are preferred in this application2O21:1, forming a conical cavity, and facilitating the subsequent formation of a needle-punched alumina material。
In addition, after the corrosion, air can be used for drying without inert atmosphere drying, and the method is mainly used for oxidizing the subsequent hole expanding treatment, and wastes resources if the inert atmosphere is used for drying.
(4) Corroding and reaming: the oxidation temperature is 700 deg.CoAnd C, forming disordered silicon oxide on the surface of the monocrystalline silicon for 30-40min, then cooling and soaking in 10-15wt% hydrofluoric acid for 10min to remove an oxide layer, and repeating the etching and reaming step for 1-3 times to obtain the large-aperture etched hole.
The sizes of silver ions are generally distributed at 10-30 nm, the aperture of the opening of the obtained pore channel is 70-200nm after corrosion, the pore channel is small for subsequent filling of alumina sol, hole expansion needs to be carried out on the pore channel, a silicon substrate is subjected to oxidation treatment at high temperature, an oxide layer is formed on the surface of the pore channel, then the oxide layer is removed through HF, the hole expansion purpose can be easily achieved, if the size of the pore channel cannot be achieved through one-time hole expansion, hole expansion can be carried out through multiple times of corrosion, and the optimal pore channel size is 1-3 mu m as shown in attached figures 3 and 4.
(5) The process of filling alumina silica sol into the corrosion hole is as follows: adding 3-5 g of pseudo-boehmite into deionized water in batches under the stirring condition, adding 1.5-2M HNO3 to obtain alumina hydrosol, continuously stirring for 2-3 h, soaking the hole-expanded base material obtained in the step (4) into the alumina sol, vacuumizing, and filling the alumina sol on the surface of the pore channel.
(6) The high-temperature roasting parameter of the step (6) is 300oDrying under nitrogen protection for 20-30min, and then 1-2oC /min-1Heating to 1100-1300 ℃, drying at constant temperature for 1-2h, and naturally cooling.
(7) Repeating the steps (5) and (6);
for reasons of high temperature calcination, the formation of gamma-Al is based on the effect of the alumina crystal form on the strength and catalytic performance of the catalyst carrier if calcination is not performed2O3Is a powder, cannot maintain a needle-like structure, and α -Al2O3Has high strength ofIn order to effectively maintain the shape of the template, α -alumina is selected as a substrate in the invention, and the roasting temperature is 1100-1300-oC, the alumina is made of gamma-Al2O3Warp of-Al2O3Transition to α -Al2O3And α -Al2O3The carrier has better low temperature activity compared with other alumina crystal forms, as shown by XRD in figure 5, the alumina after high temperature roasting is α -Al2O3The diffraction peak shape is sharp, and the crystal structure is perfect.
In addition, the steps (5) to (6) are required to be performed for a plurality of times because the alumina is shrunk due to the dehydration and the change of the crystal form during the calcination, and nitrogen is used as a shielding gas during the calcination to protect the silicon substrate template.
(8) The heating temperature for removing the silicon substrate by the fluorine gas is 35-40 DEG CoAnd C, the time is 1-2h, the silicon oxide is removed by fluorine gas, the base material is prevented from being corroded by alkali or acid, because the aluminum oxide is amphoteric oxide, α aluminum oxide has better acid and alkali resistance than the silicon base material, but the needle-like aluminum oxide tip corrosion is caused in the process of corroding the base material, so that the base material is prevented from being removed by acid and alkali, fluorine gas is used, fluorine and silicon are simply heated and are easily reacted and volatilized, and α aluminum oxide needs to be reacted with fluorine under the condition of melting high temperature, and the condition is harsh.
(9) According to the invention, nitric acid is not needed to remove Ag ions, the silver ions are used as auxiliary metals, the catalytic activity is improved, the treatment process is saved, and the obtained needle-punched alumina has the structure shown in attached figures 1 and 2.
(10) Silver ions exist on the surface of the alumina in the form of metallic silver or silver fluoride, so the amount of water used in the whole catalyst carrier is controlled during the use process so as to prevent the silver fluoride from being dissolved in the water and losing effectiveness.
The scheme of the invention has the following beneficial effects:
(1) by effectively controlling the distribution condition and the grain diameter of Ag grains on the surface of the silicon substrate, the corrosion holes with more uniform size and shape are obtained through metal catalytic corrosion.
(2) Through the reaming treatment, the directional corrosion is effectively realized, the pore volume is improved, and the subsequent coating of the alumina sol is convenient.
(3) The silicon pore channel structure is complete, the interface is clear, the pore channel is uniform, and the obtained aluminum oxide is of a needle-punched structure.
(4) The Ag metal particles do not need to be removed, are loaded on the alumina tip and can be used as an active component of gas-solid phase catalytic reaction.
Drawings
FIG. 1 is an SEM cross-sectional view of a needle-punched alumina of the present invention.
FIG. 2 is a SEM top view of a needle-punched alumina of the present invention.
FIG. 3 is a top SEM view of a silicon substrate after reaming in accordance with the present invention.
FIG. 4 is an SEM magnification of a silicon substrate after reaming according to the present invention.
FIG. 5 is an XRD pattern of α -alumina of the present invention.
Detailed Description
Example 1
A needle-punched alumina carrier comprises the following steps:
(1) pretreating a silicon-based material: cutting a monocrystalline silicon wafer to a proper size, then carrying out ultrasonic cleaning on the monocrystalline silicon wafer by ethanol, acetone and deionized water in sequence for removing oil stains for 1 time, then soaking the monocrystalline silicon wafer in 10wt% hydrofluoric acid for 10min for removing an oxide layer, washing the monocrystalline silicon wafer by deionized water, and drying the monocrystalline silicon wafer in an inert atmosphere;
(2) chemical deposition of Ag particles on silicon surface: the chemical deposition solution is aqueous solution of silver nitrate and hydrofluoric acid, the volume ratio of AgNO3 to HF to H2O is 1: 2: 4, and the temperature is 30oC, the time is 1 min;
(3) and (3) catalyzing and corroding the silicon material by Ag particles to obtain corrosion holes: the corrosive liquid is aqueous solution of hydrofluoric acid and hydrogen peroxide, the concentration of HF is 0.3M, and H is2O2The concentration of the catalyst is 0.3M, the time is 60min, the temperature is normal temperature, the ionic water is washed after corrosion, and the air is dried and oxidized;
(4) corroding and reaming the hole; the oxidation temperature is 700 deg.CoC, forming disordered silicon oxide on the surface of the monocrystalline silicon for 30min, and then reducingSoaking in 10wt% hydrofluoric acid for 10min to remove the oxide layer, and repeating the etching and reaming step for 1 time to obtain a large-aperture etched hole;
(5) filling alumina silica sol into the corrosion hole: adding 3 g of pseudo-boehmite into deionized water in batches under the stirring condition, adding 1.5M HNO3 to obtain alumina hydrosol, continuously stirring for 2 hours, soaking the hole-expanded base material obtained in the step (4) into the alumina sol, vacuumizing, and filling the alumina sol on the surface of a pore channel;
(6) and (3) high-temperature roasting: 300oDrying for 20min under the protection of nitrogen, and then 1oC /min-1Heating to 1100 ℃, drying at constant temperature for 1h, and naturally cooling;
(7) and (5) repeating the steps (5) and (6) for 2 times.
(8) The heating temperature of the fluorine gas-removed silicon substrate was 35oAnd C, the time is 1h, and the needle-like alumina carrier is obtained.
Example 2
A needle-punched alumina carrier comprises the following steps:
(1) pretreating a silicon-based material: cutting a monocrystalline silicon wafer to a proper size, then carrying out ultrasonic cleaning on the monocrystalline silicon wafer by ethanol, acetone and deionized water in sequence to remove oil stains, repeating the cleaning for 2 times, then soaking the monocrystalline silicon wafer in 12.5wt% hydrofluoric acid for 10min to remove an oxide layer, washing the monocrystalline silicon wafer by deionized water, and drying the monocrystalline silicon wafer in an inert atmosphere;
(2) chemical deposition of Ag particles on silicon surface: the chemical deposition solution is aqueous solution of silver nitrate and hydrofluoric acid, the volume ratio of AgNO3 to HF to H2O is 1: 2.5: 6, and the temperature is 32.5oC, the time is 1.5 min;
(3) and (3) catalyzing and corroding the silicon material by Ag particles to obtain corrosion holes: the corrosive liquid is aqueous solution of hydrofluoric acid and hydrogen peroxide, the concentration of HF is 0.35M, and H is2O2The concentration of the catalyst is 0.35M, the time is 70min, the temperature is normal temperature, the ionic water is washed after corrosion, and the air is dried and oxidized;
(4) corroding and reaming the hole; the oxidation temperature is 700 deg.CoC, forming disordered silicon oxide on the surface of the monocrystalline silicon for 35min, and then cooling and soakingSoaking in 12.5wt% hydrofluoric acid for 10min to remove the oxide layer, and repeating the etching and reaming steps for 2 times to obtain a large-aperture etched hole;
(5) filling alumina silica sol into the corrosion hole: adding 4g of pseudo-boehmite into deionized water in batches under the stirring condition, adding 1.75M HNO3 to obtain alumina hydrosol, continuously stirring for 2.5 h, soaking the hole-expanded base material obtained in the step (4) into the alumina sol, vacuumizing, and filling the alumina sol on the surface of the pore channel;
(6) and (3) high-temperature roasting: 300oDrying under nitrogen protection for 25min, and then 1.5oC /min-1Rise to 1200oC, drying for 1-2h at constant temperature, and naturally cooling;
(7) and (5) repeating the steps (5) and (6) for 3 times.
(8) The heating temperature of the fluorine gas-removed silicon substrate was 37oAnd C, the time is 1.5h, and the needle-like alumina carrier is obtained.
Example 3
A needle-punched alumina carrier comprises the following steps:
(1) pretreating a silicon-based material: cutting a monocrystalline silicon wafer to a proper size, then carrying out ultrasonic cleaning on the monocrystalline silicon wafer by ethanol, acetone and deionized water in sequence to remove oil stains, repeating the cleaning for 3 times, then soaking the monocrystalline silicon wafer in 15wt% hydrofluoric acid for 10min to remove an oxide layer, washing the monocrystalline silicon wafer by deionized water, and drying the monocrystalline silicon wafer in an inert atmosphere;
(2) chemical deposition of Ag particles on silicon surface: the chemical deposition solution is aqueous solution of silver nitrate and hydrofluoric acid, the volume ratio of AgNO3 to HF to H2O is 1: 3: 8, and the temperature is 35oC, the time is 2 min;
(3) and (3) catalyzing and corroding the silicon material by Ag particles to obtain corrosion holes: the corrosive liquid is aqueous solution of hydrofluoric acid and hydrogen peroxide, the concentration of HF is 0.45M, and H is2O2The concentration of the catalyst is 0.4M, the time is 80min, the temperature is normal temperature, the ionic water is washed after corrosion, and the air is dried and oxidized;
(4) corroding and reaming the hole; the oxidation temperature is 700 deg.CoC, forming disordered silicon oxide on the surface of the monocrystalline silicon for 40min, and then cooling and soakingSoaking in 15wt% hydrofluoric acid for 10min to remove the oxide layer, and repeating the etching hole-expanding step for 3 times to obtain a large-aperture etched hole;
(5) filling alumina silica sol into the corrosion hole: adding 5 g of pseudo-boehmite into deionized water in batches under the stirring condition, adding 2M HNO3 to obtain alumina hydrosol, continuously stirring for 3 h, soaking the reamed base material obtained in the step (4) into the alumina sol, vacuumizing, and filling the alumina sol on the surface of the pore channel;
(6) and (3) high-temperature roasting: 300oDrying for 30min under the protection of nitrogen, and then 2oC /min-1Heating to 1300 ℃ and drying at constant temperature for 2h, and naturally cooling;
(7) and (5) repeating the steps (5) and (6) for 4 times.
(8) The heating temperature of the fluorine gas-removed silicon substrate was 40 deg.CoAnd C, the time is 2 hours, and the needle-punched alumina carrier is obtained.
The distribution of the needling of the needled alumina was found to be 20-40 pieces/μm by the sample tests and statistics of examples 1-3215-25nm of needling tip, 130-150nm of distance between adjacent needling tips, 5-8 μm of alumina needling height and 10-13 m of specific surface area2/g。
Although the present invention has been described above by way of examples of preferred embodiments, the present invention is not limited to the specific embodiments, and can be modified as appropriate within the scope of the present invention.
Claims (10)
1. A needle-punched alumina carrier is characterized in that the needle-punched distribution of the needle-punched alumina is 20-40 per mu m215-25nm of needling tip, 130-150nm of distance between adjacent needling tips, 5-8 μm of alumina needling height and 10-13 m of specific surface area2The alumina carrier is prepared by a template method, and silver or silver fluoride particles are attached to the vicinity of the tip of the alumina.
2. The needle-punched alumina support of claim 1, wherein the template method is prepared by the following steps: (1) pretreating a silicon-based material; (2) chemically depositing Ag particles on the surface of the silicon; (3) catalyzing and corroding a silicon material by Ag particles to obtain corrosion holes; (4) corroding and reaming the hole; (5) filling alumina silica sol into the corrosion hole; (6) roasting at high temperature; (7) repeating the steps (5) and (6); (8) the fluorine gas removes the silicon substrate.
3. The needled alumina support of claim 2, wherein the pretreatment of the silica-based material in step (1) is carried out by the following steps: cutting a monocrystalline silicon wafer to a proper size, then carrying out ultrasonic cleaning by ethanol, acetone and deionized water in sequence to remove oil stains, repeating the cleaning for 1-3 times, then soaking for 10min by 10-15wt% of hydrofluoric acid to remove an oxide layer, washing by deionized water, and drying under an inert atmosphere.
4. The alumina supporter with needle-like structure as claimed in claim 2, wherein the process of step (2) for chemically depositing Ag particles on the silicon surface is as follows: the chemical deposition liquid is water solution of silver nitrate and hydrofluoric acid, the volume ratio of AgNO3 to HF to H2O is 1: 2-3: 4-8, and the temperature is 30-35oC, the time is 1-2 min.
5. The needled alumina support of claim 2, wherein the Ag particles of step (3) catalyze corrosion of the silica material by the following process parameters: the corrosive liquid is aqueous solution of hydrofluoric acid and hydrogen peroxide, the concentration of HF is 0.3-0.45M, and H is2O2The concentration of the catalyst is 0.3-0.4M, the time is 60-80min, the temperature is normal temperature, the catalyst is washed by ionized water after being corroded, and the catalyst is dried and oxidized by air.
6. A needle-punched alumina support as claimed in claim 2, wherein the corrosion pore-enlarging parameters of step (4) are as follows: the oxidation temperature is 700 deg.CoC, forming disordered silicon oxide on the surface of the monocrystalline silicon for 30-40min, then cooling and soaking in 10-15wt% hydrofluoric acid for 10min to remove the oxide layer, wherein the step of etching and reaming can be repeated for 1-3 times to obtain a large-aperture etched hole。
7. A needle-punched alumina support as claimed in claim 2, wherein step (5) of filling the etched pores with the alumina silica sol is carried out by: adding 3-5 g of pseudo-boehmite into deionized water in batches under the stirring condition, adding 1.5-2M HNO3 to obtain alumina hydrosol, continuously stirring for 2-3 h, soaking the hole-expanded base material obtained in the step (4) into the alumina sol, vacuumizing, and filling the alumina sol on the surface of the pore channel.
8. The needled alumina support of claim 2 wherein the high temperature calcination parameter of step (6) is 300oDrying under nitrogen protection for 20-30min, and then 1-2oC /min-1Heating to 1100-1300 ℃, drying at constant temperature for 1-2h, and naturally cooling.
9. The needled alumina support of claim 2 wherein the fluorine gas removal silica substrate of step (8) is heated at a temperature of from 35 to 40 deg.CoC, the time is 1-2 h.
10. Use of a needle-punched alumina support according to any of claims 1 to 9, characterized in that it is used in the field of supports for gas-solid phase catalytic reactions.
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